Ir(ppy)(2)(H(2)dcbpy)PF6 (IrHP, ppy = 2-phenylpyridine, H(2)dcbpy = 4,4'-dicarboxy-2,2'-bipyridine) as the bridging ligand mixed with Zn(NO3)(2)center dot 6H(2)O in a ratio of 1:2 (ZnIrHP) in PMMA discs has been synthesized. The two-photon excitation emission of IrHP and ZnIrHP is ascribed to a (MLCT)-M-3 transition. The two-photon absorption (2PA) cross section and two-photon induced excited state absorption (ESA) cross section of IrHP were deduced as 1.37 x 10(4) +/-6.87 x 10(2) GM and 6.63 x 10(-22) +/- 3.31 x 10(-23) cm(2), respectively, at 800 nm (1 GM = 10(-50) cm(4) s/photon). In contrast, the 2PA of ZnIrHP exhibits higher-order nonlinearity and the cross section was 5.68 x 10(5) +/- 2.84 x 10(4) GM. (C) 2011 Elsevier B.V. All rights reserved.